Giant and Nonvolatile Control of Exchange Bias in Fe3GeTe2/Irradiated Fe3GeTe2/MgO Heterostructure Through Ultralow Voltage

The discovery of van der Waals magnets has provided a new platform for the electrical control of magnetism. Recent experiments have demonstrated that the magnetic properties of van der Waals magnets can be tuned by various gate modulations, although most of them are volatile and require gate voltages no lower than several volts. Here, the realization of nonvolatile control of exchange bias and coercive fields in Fe₃GeTe₂/MgO heterostructures, and the gate voltage is as low as tens of mV which is two orders of magnitude smaller than those in previous experiments is presented. The discovery of an ionic-irradiated phase formed in Fe₃GeTe₂ by MgO sputtering revealed that an exchange bias effect can be obtained in this heterostructure and tuned from ≈700 to 0 Oe through voltages ranging from 5 to 20 mV. Owing to the high stability of oxidized Fe₃GeTe₂, the voltage-driven oxygen incorporated into Fe₃GeTe₂ from the irradiated phase induces a nonvolatile magnetism modulation that can be retained after turning off the gate voltage. These findings demonstrate a methodology to modulate the magnetism of van der Waals magnets, opening new opportunities to fabricate all-solid, long-retention, and low-dissipation nano-electronic devices using van der Waals materials.     

Direct Growth of Germanene at Interfaces between Van der Waals Materials and Ag(111)

Germanene, a 2D honeycomb germanium crystal, is grown at graphene/Ag(111) and hexagonal boron nitride (h-BN)/Ag(111) interfaces by segregating germanium atoms. A simple annealing process in N₂ or H₂/Ar at ambient pressure leads to the formation of germanene, indicating that an ultrahigh-vacuum condition is not necessary. The grown germanene is stable in air and uniform over the entire area covered with a van der Waals (vdW) material. As an important finding, it is necessary to use a vdW material as a cap layer for the present germanene growth method since the use of an Al₂O₃ cap layer results in no germanene formation. The present study also proves that Raman spectroscopy in air is a powerful tool for characterizing germanene at the interfaces, which is concluded by multiple analyses including first-principles density functional theory calculations. The direct growth of h-BN-capped germanene on Ag(111), which is demonstrated in the present study, is considered to be a promising technique for the fabrication of future germanene-based electronic devices.     

Manipulation of Magnetic Skyrmion in a 2D van der Waals Heterostructure via Both Electric and Magnetic Fields

As a promising candidate for the much-desired low power consumption spintronic devices, 2D magnetic van der Waals material also provides a versatile platform for the design and control of topological spin textures. In this work on WTe₂/CrCl₃ bilayer van der Waals heterostructures, a complete Néel-type skyrmion–bimeron–ferromagnet phase transition is demonstrated, accompanied by the evolution of the topological number. This cyclic transition, mediated by a perpendicular magnetic field, is largely driven by the competition between the out-of-plane magnetocrystalline anisotropy and magnetic dipole–dipole interaction. In the presence of a driving current, the Néel-type skyrmion gains a higher velocity yet larger skyrmion Hall angle, in comparison to the bimeron. By incorporating a ferroelectric CuInP₂S₆ monolayer as a substrate, writing and erasing of skyrmions may be regulated using a ferroelectric polarization. This work sheds light on a novel approach to the design and control of magnetic skyrmions on 2D van der Waals materials.     

Manipulating Spin Exchange Interactions and Spin-Selected Electron Transfers of 2D Metal Phosphorus Trisulfide Crystals for Efficient Oxygen Evolution Reaction

Because oxygen molecules in the ground state favor a triplet spin configuration, spin-polarized electrons at electrocatalysts may promote the generation of parallel spin-aligned oxygen atoms, enhancing oxygen evolution reaction (OER) kinetics. In this study, a significant enhancement of OER performance is demonstrated by controlling the spin-exchange interaction and spin-selected electron transfer of 2D Co_xFe_1−xPS₃ (x = 0–0.45) van der Waals (vdW) single crystals through Co doping. The pristine FePS₃ exhibits antiferromagnetic orbital ordering, while the Co-doped FePS₃ exhibits the emergence of interatomic ferromagnetism due to doping-mediated magnetic exchange interactions. The coupling between Fe and Co ions in the Co-doped FePS₃ crystal allows the formation of efficient spin-selective electron transfer channels compared to the pristine FePS₃. The correlation of spin-exchange interactions and spin-selected electron transfers of 2D Co-doped FePS₃ crystals with a superior OER performance is further revealed by superconducting quantum interference device magnetometer, in situ X-ray absorption near edge spectra and density functional theory simulations. The result suggests that manipulating the spin-exchange interactions of 2D vdW crystals to enhance the spin-selected electron transfer efficiencies through doping is an effective strategy to boost their OER catalytic performances.     

Impact of Bonding on the Stacking Defects in Layered Chalcogenides

Phase‐change materials for high‐density data storage traditionally exploit the amorphous‐to‐crystalline phase transition. A number of these compounds are organized in blocks, separated by van der Waals‐like gaps. Such layered chalcogenides are attracting interest due to their unique material properties and the possibility to change their properties upon local rearrangements at the gap, giving rise to novel applications. To better understand the behavior of layered chalcogenides, the connection between structural defects, physical properties, and the bonding situation is highlighted here using electron microscopy, X‐ray diffraction, and density functional theory. In particular, stacking defects in hexagonal Ge₄Se₃Te, GaSe, and Sb₂Te₃ are characterized experimentally, followed by an investigation of the influence of observed and hypothetical stacking defects on optical and electronic properties by theoretical means. Then, a connection between observed defects and the bonding situation in these materials is drawn and related to the presence of van der Waals and metavalent bonding in chalcogenides. Finally, additional experiments are performed to validate the conclusions for other metavalently bonded layered chalcogenides. Transmission electron microscopy provides a powerful tool for direct detection of defects and, when combined with diffraction experiments and ab initio theory, it facilitates the precise investigation of the bonding mechanisms in layered chalcogenides.     

E‐Field Control of Exchange Bias and Deterministic Magnetization Switching in AFM/FM/FE Multiferroic Heterostructures

The coexistence of electrical polarization and magnetization in multiferroic materials provides great opportunities for novel information storage systems. In particular, magnetoelectric (ME) effect can be realized in multi­ferroic composites consisting of both ferromagnetic and ferroelectric phases through a strain mediated interaction, which offers the possibility of electric field (E‐field) manipulation of magnetic properties or vice versa, and enables novel multiferroic devices such as magnetoelectric random access memories (MERAMs). These MERAMs combine the advantages of FeRAMs (ferroelectric random access memories) and MRAMs (magnetic random access memories), which are non‐volatile magnetic bits switchable by electric field (E‐field). However, it has been challenging to realize 180° deterministic switching of magnetization by E‐field, on which most magnetic memories are based. Here we show E‐field modulating exchange bias and for the first time realization of near 180° dynamic magnetization switching at room temperature in novel AFM (antiferromagnetic)/FM (ferromagnetic)/FE (ferroelectric) multiferroic heterostructures of FeMn/Ni₈₀Fe₂₀/FeGaB/PZN‐PT (lead zinc niobate–lead titanate). Through competition between the E‐field induced uniaxial anisotropy and unidirectional anisotropy, large E‐field‐induced exchange bias field‐shift up to $ {{{\Delta H_{ex}}}\over{{H_{ex}}}} = 218\%$ and near 180° deterministic magnetization switching were demonstrated in the exchange‐coupled multiferroic system of FeMn/Ni₈₀Fe₂₀/FeGaB/PZN‐PT. This E‐field tunable exchange bias and near 180° deterministic magnetization switching at room temperature in AFM/FM/FE multiferroic heterostructures paves a new way for MERAMs and other memory technologies.     

Meta‐Stable Molecular Configuration Enables Thermally Stable and Solution Processable Organic Charge Transporting Materials

The construction of state‐of‐the‐art charge transporting materials (CTMs) is challenging in modulating molecular configurations for simultaneously achieving high thermal stability and appreciable solution processability. Herein, N,N′‐bis(1‐indanyl)naphthalene‐1,4,5,8‐tetracarboxylic diimide (NDI‐ID) is served as a theoretical model to investigate the influence of molecular structure on the tradeoff between thermal stability and solubility. Compared with the alkyl substituted analog, the thermal stability of NDI‐ID is enhanced by the intramolecular and intermolecular short contacts, indicating the conformational rigidity dictates the morphological stability of the film phase. On the other hand, the dynamic topological transformation of material molecules occurs during the solvation process and, where the intramolecular hydrogen bonds are attenuated by the interactions with the surrounding solvent, leads to the increased solubility. The meta‐stable molecular configuration endows NDI‐ID a favorable union of superior solution processability and higher thermal stability, and this insight is also perfectly exemplified by the newly designed CTMs. Therefore, these results reveal the significant role of structural dynamics on material properties, which can provide a new train of thought to develop CTMs for highly efficient and stable perovskite solar cells.     

van der Waals Epitaxial Growth of Atomically Thin 2D Metals on Dangling‐Bond‐Free WSe2 and WS2

2D metals have attracted considerable recent attention for their special physical properties, such as charge density waves, magnetism, and superconductivity. However, despite some recent efforts, the synthesis of ultrathin 2D metals nanosheets down to monolayer thickness remains a significant challenge. Herein, by using atomically flat 2D WSe₂ or WS₂ as the growth substrate, the synthesis of atomically thin 2D metallic MTe₂ (M = V, Nb, Ta) single crystals with the thickness down to the monolayer regime and the creation of atomically thin MTe₂/WSe₂ (WS₂) vertical heterojunctions is reported. Comparison with the growth on the SiO₂/Si substrate under the same conditions reveals that the utilization of the dangling‐bond‐free WSe₂ or WS₂ as the van der Waals epitaxy substrates is crucial for the successful realization of atomically thin MTe₂ (M = V, Nb, Ta) nanosheets. It is further shown that the epitaxial grown 2D metals can function as van der Waals contacts for 2D semiconductors with little interface damage and improved electronic performance. This study defines a robust van der Waals epitaxy pathway to ultrathin 2D metals, which is essential for fundamental studies and potential technological applications of this new class of materials at the 2D limit.     

氯溴双卤代烷烃分子构型和光谱对烷基链长依赖关系的研究

氯溴双卤代烷烃在太阳紫外光辐射下解离生成游离态的氯和溴自由基,它们是破坏臭氧的主要元凶之一。利用B3LYP/6-311++G(d,p)方法对氯溴双卤代烷烃分子CnH2nBrCl(n=1~16)进行分子构型优化以及红外光谱的计算。根据数据进行分析比较,得到了氯溴双卤代烷烃C-Br键和C-Cl键的键长、键角等构型参数随烷基支链长度增加(n为1~16)的变化趋势图。研究讨论了氯溴双卤代烷烃的红外光谱相关振动随烷基支链长度增加的重要变化规律。     

Nonfullerene Small‐Molecule Acceptors for Organic Photovoltaics: Understanding the Impact of Methoxy Substitution Position on Molecular Packing and Electron‐Transfer Properties

Nonfullerene small‐molecule acceptors (SMAs) are considered as a key component of next‐generation organic photovoltaics. Introducing functional groups to the end‐groups of “acceptor‐donor‐acceptor”‐type SMAs is a facile and convenient way to tune their optoelectronic and morphological properties. Here, molecular dynamics simulations are combined with long‐range corrected density functional theory calculations to explore the molecular‐scale impact that the position of methoxy substitution in the end‐group has on the molecular packing and electron‐transfer properties in neat films. The focus here is on 3,9‐bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(4‐hexylphenyl)‐dithieno [2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene (IT‐OM), where three end‐group methoxy substitution positions are evaluated. Changing the methoxy substitution position is found to influence, to different extents, the planarity of the end‐groups and thus the intermolecular packing density. The effect on the intermolecular electron‐transfer rates is also examined and leads to markedly different sizes of strongly interconnected clusters. Overall, these findings are fully consistent with the experimental evolution of electron mobility in the neat IT‐OM film as a function of methoxy substitution position.     

Bulk Heterojunction Solar Cells: Impact of Minor Structural Modifications to the Polymer Backbone on the Polymer–Fullerene Mixing and Packing and on the Fullerene–Fullerene Connecting Network

The morphology of the active layer of a bulk heterojunction solar cell, made of a blend of an electron‐donating polymer and an electron‐accepting fullerene derivative, is known to play a determining role in device performance. Here, a combination of molecular dynamics simulations and long‐range corrected density functional theory calculations is used to elucidate the molecular‐scale effects that even minor structural changes to the polymer backbone can have on the “local” morphology; this study focuses on the extent of polymer–fullerene mixing, on their packing, and on the characteristics of the fullerene–fullerene connecting network in the mixed regions, aspects that are difficult to access experimentally. Three representative polymer donors are investigated: (i) poly[(5,6‐difluoro‐2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PffBT4T‐2OD); (ii) poly[(2,1,3‐benzothiadiazol‐4,7‐diyl)‐alt‐(3,3′″‐di(2‐octyldodecyl)‐2,2′;5′,2″;5″,2′″‐quaterthiophen‐5,5′″‐diyl)] (PBT4T‐2OD), where the fluorine atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with hydrogen atoms; and (iii) poly[(2,2′‐bithiophene)‐alt‐(4,7‐bis((2‐decyltetradecyl)thiophen‐2‐yl)‐5,6‐difluoro‐2‐propyl‐2H‐benzo[d][1,2,3]triazole)] (PT2‐FTAZ), where the sulfur atoms in the benzothiadiazole moieties of PffBT4T‐2OD are replaced with nitrogen atoms carrying a linear C₃H₇ side‐chain; these polymers are mixed with the phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) acceptor. This study also discusses the nature of the charge‐transfer electronic states appearing at the donor–acceptor interfaces, the electronic couplings relevant for the charge‐recombination process, and the electron‐transfer features between neighboring PC₇₁BM molecules.     

表面单分子的表征和操纵

本文对国内外表面单分子的表征和操纵的研究概况进行了简短评述,重点介绍了我们的一些基础研究结果,结合扫描隧道显微术和电子密度泛函理论模拟,在单分子C60的高分辨表征、C60在Si表面的吸附取向、富勒烯分子Dy@C82的空间和能量分辨、Pd纳米颗粒的无序抑制量子限域效应,制备基于C60的负微分电导和C59N的分子整流器件及单个CoPc分子自旋性质的调控等方面取得一些较重要的进展。     

Solvent-Driven Transformation of Microsized Metal Particles into a Nanoporous Structure and Its Application to Ultrafast-Charging Batteries

The coalescence of metal nanoparticles in colloidal solutions is a universal and ubiquitous phenomenon. Using this behavior, a simple yet effective route is developed that enables the spontaneous transformation of microsized metals into nanoporous structures in specific electrolyte solvents. The criteria for selecting solvents and counterpart metals suitable for generating nanoporous structures are derived based on the classical theory of acid–base reactions and quantum chemistry based on density functional theory. When employing the developed method for anodes for Na-ion batteries, the anodes prepared using microsized Sn, Pb, Bi, and CuS particles store 592, 423, 383, and 546 mAh g⁻¹, respectively, at 10 C with cycling lifetimes of 3000−6000 cycles. This study provides fundamental framework for selecting solvents to realize low-cost anodes with large capacities, long cycling lifetimes, and excellent rate performances. Moreover, the findings can be extended to other functional materials that can exploit their large specific surface areas.     

表面结构和生长方向对WO3纳米线电子结构影响的第一性原理研究

The effects of the surface and orientation of a WO₃ nanowire on the electronic structure are investigated by using first principles calculation based on density functional theory（DFT）.The surface of the WO3 nanowire was terminated by a bare or hydrogenated oxygen monolayer or bare WO₂ plane,and the[010]- and[001]-oriented nanowires with different sizes were introduced into the theoretical calculation to further study the dependence of electronic band structure on the wire size and orientation.The calculated results reveal that the surface structure, wire size and orientation have significant effects on the electronic band structure,bandgap,and density of states （DOS） of the WO₃ nanowire.The optimized WO₃ nanowire with different surface structures showed a markedly dissimilar band structure due to the different electronic states near the Fermi level,and the O-terminated[001] WO₃ nanowire with hydrogenation can exhibit a reasonable indirect bandgap of 2.340 eV due to the quantum confinement effect,which is 0.257 eV wider than bulk WO₃.Besides,the bandgap change is also related to the orientation-resulted surface reconstructed structure as well as wire size.     

Theoretical insight into the electronic and photocatalytic properties of Cu2O from a hybrid density functional theory

A comprehensive first-principle investigation, based on hybrid density functional theory, produces strong evidence that the Cu₂O band-edges do satisfy the requirements of the H⁺/H₂ and O₂/H₂O redox levels, demonstrating that it has enough driving force for photocatalytic overall water splitting. The calculated band gap of Cu₂O is 2.184 eV, which is consistent with the experimental value of 2.17 eV. The highly dispersive s–s hybrid states at the conduction band bottom result in a small effective mass of the electron, which is favorable to carrier separation and the carrier transfer to surface, and thus facilitate the reduction of H⁺ to H₂. The strong optical absorption of Cu₂O is beneficial to overall water splitting under visible light irradiation. Possible reasons for no observation of H₂ in some experiments are also discussed. The results address the ongoing controversy associated with photocatalytic overall water splitting of Cu₂O.     

Growth and Raman Scattering Investigation of a New 2D MOX Material: YbOCl

MOX (M = Fe, Co, Mn, Cr, Lanthanide, or Actinide metals; O = oxygen, X = F, Cl, Br, I), an emerging type of 2D layered materials, have been theoretically predicted to possess unique electronic and magnetic properties. However, 2D MOX have rarely been investigated. Herein, for the first time, ultrathin high‐quality ytterbium oxychloride (YbOCl) single crystals are successfully synthesized via an atmospheric pressure chemical vapor deposition method. Both theoretical simulations and experimental measurements are utilized to systematically investigate the Raman properties of 2D YbOCl nanosheets. The experimentally observed E_g mode at 85.53 cm^?1 and A_1g mode at 138.17 cm^?1 demonstrate a good match to the results from density functional theory calculations. Furthermore, the temperature‐dependent and thickness‐dependent Raman scattering spectra reveal the adjacent layers in YbOCl nanosheets show a relatively weak van der Waals interaction. Additionally, the polarized‐dependent Raman scattering spectra show the intensity of A_1g mode exhibits twofold patterns while the intensity of the E_g mode remains constant as the rotation angle changes. These findings could provide the first‐hand experimental information about the 2D YbOCl crystals.     

有机紫外半导体PMTC的制备及理论计算研究

进行了有机紫外半导体N-[5-甲基-1,3,4-噻二唑-2-取代]二硫代氨基甲酸钾(PMTC)的制备及FT-IR、Raman、UV-Vis及PL光谱实验表征。对实验测试FT-IR及Raman光谱的振动峰进行了归属,Raman光谱测试发现S-K在152 cm-1有v(S-K-S)伸缩振动。UV-Vis实验光谱表明PMTC在200～350nm波段有紫外吸收,PL实验光谱表明PMTC在340～400 nm波段有明显的紫外发光峰,峰值波长为373 nm,PL谱相对于吸收光谱有Stokes频移。采用密度泛函理论(DFT)方法对PMTC进行了B3LYP/6-31G水平上的分子结构优化、UV-Vis光谱、分子前线轨道、分子电子密度、Mulliken电荷等理论计算。理论研究结果表明:PMTC在UV-Vis波段有三个电子跃迁吸收。前线轨道计算表明PMTC的HOMO的电子主要分布在与K原子相连的两个S原子上,而LUMO轨道的电子主要集中在K原子上,PMTC吸收光子后,产生电子由HOMO至LUMO跃迁的实质是电子由配体(主要是配位S原子)向金属原子K的转移。     

Impact of the Nature of the Side‐Chains on the Polymer‐Fullerene Packing in the Mixed Regions of Bulk Heterojunction Solar Cells

Polymer‐fullerene packing in mixed regions of a bulk heterojunction solar cell is expected to play a major role in exciton‐dissociation, charge‐separation, and charge‐recombination processes. Here, molecular dynamics simulations are combined with density functional theory calculations to examine the impact of nature and location of polymer side‐chains on the polymer‐fullerene packing in mixed regions. The focus is on poly‐benzo[1,2‐b:4,5‐b′]dithiophene‐thieno[3,4‐c]pyrrole‐4,6‐dione (PBDTTPD) as electron‐donating material and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) as electron‐accepting material. Three polymer side‐chain patterns are considered: i) linear side‐chains on both benzodithiophene (BDT) and thienopyrroledione (TPD) moieties; ii) two linear side‐chains on BDT and a branched side‐chain on TPD; and iii) two branched side‐chains on BDT and a linear side‐chain on TPD. Increasing the number of branched side‐chains is found to decrease the polymer packing density and thereby to enhance PBDTTPD–PC₆₁ BM mixing. The nature and location of side‐chains are found to play a determining role in the probability of finding PC₆₁BM molecules close to either BDT or TPD. The electronic couplings relevant for the exciton‐dissociation and charge‐recombination processes are also evaluated. Overall, the findings are consistent with the experimental evolution of the PBDTTPD–PC₆₁BM solar‐cell performance as a function of side‐chain patterns.     

Holographic Recording and Hierarchical Surface Patterning on Periodic Submicrometer Pillar Arrays of Azo Molecular Glass via Polarized Light Irradiation

Periodic submiocrometer pillar arrays are fabricated from a photoresponsive azo molecular glass (IA‐Chol) by soft‐lithographic hot embossing with elastomeric poly(dimethylsiloxane) (PDMS) modes. Through deformation of each submicrometer‐sized pillar in response to the local amplitude and polarization of the superimposed electric waves, optical holograms are recorded on the IA‐Chol pillar arrays. When the interference pattern is formed by two polarized beams with opposite‐circular polarizations, the recorded patterns mainly reflect the polarization state variations with spatial phase difference of the interfering waves. When two plane waves with the same linear polarizations are superimposed, where the polarization direction is almost the same as the writing beams, the intensity variation of the superimposed electric waves is recorded by the pillar arrays changing spatially with the phase variations. Various ordered surface patterns with distinct hierarchical configurations are successfully developed by the intensity and polarization modulations of the interfering waves. This approach not only allows to directly visualize the intensity and polarization of the coherent light captured by the holograms, but also provides a powerful platform to fabricate various complex surface patterns. The submicrometer pillar arrays can also be used to record polarization hologram and the images are reconstructed by reference light in diffracted spots.     

单晶硅表面STM成像理论模型与实验分析

结合扫描隧道显微镜(STM)成像实验和第一性原理原子级模拟计算的方法已经成为材料界面表征的重要手段。超高真空条件下的STM可用于直接观察单原子等微观结构,但其成像原理还未被理解清楚。STM扫描测得的试件表面原子级图像并不直接反映材料原子的形态,实际上是表面形貌和表面电子态局域密度的综合结果。为了解释STM成像,采用第一性原理Siesta方法,研究了Si(001)面STM成像过程的电子结构,对表面粒子的原子轨道和相应的电荷密度进行计算。讨论了等高模式下扫描高度对局域电子云密度分布的影响,并分析了STM针尖几何形状对模拟结果的影响。研究表明,材料表面原子的电子云密度分布可以用来解释STM成像精度和扫描高度对比的变化。